JPH01150130A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To increase the progression of development of a photosensitive material and to prevent the degradation of film quality in a wet state by incorporating a specific polymer and/or dextran and prescribed cationic compd. into said material. CONSTITUTION:The title photosensitive material is formed by adding the polymer contg. the repeating unit expressed by the formula I and/or dextran to, for example, an emulsion layer and adding the cationic compd. (A) contg. quaternary nitrogen to the emulsion layer or the lowermost layer, etc. In the formula, R<1> denotes H, alkyl of 1-6C; R<2>, R<3> denote H, (substd.)alkyl of -10C, etc.; L denotes a combination group of m+1 valency; n denotes 0, 1; m denotes 1, 2. A compd. contg. an alkyl group or alkenyl group or alkylene group of 6-18C as a hydrophobic group is usable for the compd. A and the compd. expressed by the formula II is usable for the same.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a highly sensitive silver halide photographic light-sensitive material, and particularly to a silver halide photographic light-sensitive material which exhibits extremely fast development progress and excellent film quality.

(Prior Art) In general, in silver halide photographic materials, it is important to improve development progress from the viewpoint of increasing sensitivity and speeding up processing.

Silver bromide emulsions are used in high-sensitivity photographic materials due to the trade-off between sensitivity and image quality, but such emulsions are particularly slow in development compared to silver chloride or silver bromide, and it is difficult to improve this. The big question was whether to do so.

As a way to solve this problem, there is a long-established US patent! ,1
No. 723.189, No. 2.13/, No. 132, No. J,
13! Although a method of adding a nonionic surfactant having a polyoxyethylene group to an emulsion is known, as described in No. 220, this technique alone was insufficient to meet the demand for further speeding up processing.

It has been known that polyacrylamides and dextrans are used to improve the progress of development, as described in JP-A No. 4/12O61. However, when these polymers are added, the film quality in a wet state is significantly deteriorated (for example, the traction strength in a wet state is reduced), which has been a problem.

Also, until now, JP-A-413-1μOλj, % Kaisho! 2-
/117321r% It has been known that development progresses faster when a cationic compound is present as described in JP-A-74-/J-6126 and JP-B Sho≠t-μ3134.

However, it was impossible to predict that using both in combination would solve the problem of deterioration in film quality in a wet state due to the addition of a polymer.

(Objective of the Invention) It is an object of the present invention to provide a silver halide photographic material which has improved development progress and excellent film quality in a wet state.

(Structure of the Invention) The above aspects of the present invention provide a silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer on at least one side of a support, the light-sensitive material having the following general formula ( A silver halide photograph comprising a polymer containing a repeating unit represented by II) and/or a text run, and containing a cationic compound containing μ-class nitrogen in the photographic emulsion layer or other constituent layers. This could be achieved using photosensitive materials.

General formula (n) R'' (wherein R is a hydrogen atom or an alkyl group having 7 to 6 carbon atoms, R is a hydrogen atom, a substituted or unsubstituted alkyl group having 10 or less carbon atoms, respectively. - represents an aralkyl group or an aralkyl group, which may be the same or different.
R and R may be bonded to each other to form a nitrogen-containing heterocycle together with the nitrogen atom. L is a linking group with m+/valence. n is O
or l, and m is 1 or λ. ) The effects of the present invention are believed to be due to the effect of preventing the diffusion of the polymer containing repeating units represented by the general formula (II) and/or dextran or phase separation from gelatin by the cationic compound containing fringe nitrogen.

Preferred polymers of the present invention having repeating units represented by general formula (II) are shown below.

In general formula (II), R1 is a hydrogen atom or carbon number/~
represents an alkyl group, preferably a hydrogen atom or a methyl group.

R and R each represent a hydrogen atom, a substituted or unsubstituted alkyl group having 10 or less carbon atoms, an aryl group or an aralkyl group, and may be the same or different. Examples of the substituent include a hydroxyl group, a lower alkoxy group, a halogen atom, an amide group, a cyano group, a sulfonic acid group, and a carboxylic acid group.几 and 几 are preferably a hydrogen atom, a methyl group, an ethyl group, or a phenyl group, and among them, a hydrogen atom is most preferable.

L represents a covalent linking group, an example of which is carbon number/-7
Examples thereof include zero alkylene groups, arylene groups, or covalent groups obtained by combining them with ether bonds, ester bonds, amide bonds, etc.

n represents O or l, with O being preferred.

m represents 1 or 0, and 1 is preferred.

Among the ethylenically unsaturated monomers constituting the repeating unit represented by general formula (n), specific examples of preferred ones are listed below.

1-/ ■−− CH2=C)] C0NHCH3 CH2=CH C0NHC2H5 B-Hiroshi CH2=CH C0NHC2H 5-s ]]-7 C0N)i2 ■－／／ 11-/≠ 1-/j ■-/6 ■-77 CH2=CH C0N)Ic(CH3) 2 1-x.

The repeating unit represented by the general formula (n) may contain two or more types of monomer units in order to exhibit a composite function as a polymer.

The high molecular weight polymer in the present invention contains a monomer represented by the general formula (If) as a polymer constituent unit in an amount of 70 mol% or more, preferably ♂O mol% or more, and more preferably 0 mol%.
This is a compound represented by the following general formula (III) including the above.

General formula (In) (1) In the formula, X represents a molar percentage, and preferably 70 to 100.

The person in the formula represents a monomer unit copolymerized with a copolymerizable ethylenically unsaturated monomer.

Examples of ethylenically unsaturated monomers in the preferred polymers of the invention are ethylene, propylene, l-butene, imbutene, styrene, chloromethylstyrene, hydroxymethylstyrene, sodium vinylbenzenesulfonate, sodium vinylbenzylsulfonate, N, N, N-trimethyl-N-vinylbenzylammonium chloride, N,
N-dimethyl-N-benzyl-N-vinylbenzylammonium chloride, α-methylstyrene, vinyltoluene, darvinylpyridine, covinylpyridine, benzylvinylpyridinium chloride, N-vinylacetamide, N-vinylpyrrolidone, l-vinylpyridine - methylimidazole, monoethylenically unsaturated esters of aliphatic acids (e.g. vinyl acetate, allyl acetate), ethylenically unsaturated mono- or dicarboxylic acids and their salts (e.g. acrylic acid, methacrylic acid, itaconic acid, maleic acid) , sodium acrylate, potassium acrylate, sodium methacrylate), maleic anhydride, esters of ethylenically unsaturated monocarboxylic or dicarboxylic acids (
For example, n-butyl acrylate, n-hexyl acrylate, hydroxyethyl acrylate, cyanethyl acrylate, N.

N-diethylamine ethyl acrylate, methyl methacrylate, n-butyl methacrylate, benzyl methacrylate, hydroxyethyl methacrylate, chloroethyl methacrylate, methoxyethyl methacrylate,
N, N-diethylaminoethyl methacrylate), N, N
, N-)diethyl-N-methacryloyloxyethylammonium p-toluenesulfonate, N,N-diethyl-N-methyl-N-methacryloyloxyethylammonium p-toluenesulfonate, dimethyl itaconate, maleic acid monobenzyl ester) In addition to , etc.
Tokukai Akira! 6-1! IP37, JP-A-Sho J-7-10 Hiroki λ
7. Tokukai Sho t+-i4! Examples include gelatin-reactive monomers disclosed in RZ-μ and others. Further, the stack of the present invention may contain two or more heptad units as A in order to exhibit a composite function.

Preferred examples of compounds for the 'rIL complex in the present invention include the following. (Numbers represent mole percentages.) Compound examples (P-/) (P-2) (P-7) H3 - (P-Hiroshi) (P-z) (p-+) (P-7) ( pr) (P-ta) (P-//) H3 ■ (P-/ko) (P-/J) (P-/≠) CONH2 General formula (n) added to the photographic emulsion layer in the present invention A polymer having repeating units represented by M total average molecule i
(MW) is r, ooo to 20o, ooo preferably 7
．． 000 to 100,000, more preferably /j, 0
00 to 70,000 is good. The amount i of such a polymer added can be selected arbitrarily, but the optimum amount added to increase the covering power varies depending on the type of photographic emulsion.

In the present invention, the text run added to the photographic emulsion layer is
Dextran-producing bacteria such as Leuconostoc mesenteroides, or dextran sucrase isolated from the culture broth of these bacteria, is applied to a recommended sugar solution, and the resulting native dextran is partially decomposed by acid and alkaline fermentation.
The molecular weight has been legally reduced. The weight average molecular weight of the text run used in the present invention is from 10,000 to 3θo, ooo, preferably /! , θ00 to 10o
, ooo, more preferably 20,000 to 70.00
It is 0.

The polymer and/or dextran having a repeating unit represented by the general formula (n) used in the present invention accounts for the entire binder in the photographic emulsion. ~jOM amount%, especially IO−≠
It is preferable to add so that the amount of ON becomes %.

The polymer used in the present invention may be contained in any photographic emulsion layer, but it is preferably contained in all photographic emulsion layers.

More preferably, the polymer density in the photographic emulsion layer adjacent to the support (polymer i of the polymer used in the present invention/binder weight of the layer to which the polymer is added) is lower than the polymer density in other photographic emulsion layers. The smaller the better.

Even better results can be obtained if the non-photosensitive gelatin layer adjacent to the photographic emulsion NK also contains the polymer of the present invention.

When the polymer of the present invention is added to each layer of a photographic material, it is preferred that the binder ratio of the polymer/added layer is not significantly different from that of the adjacent layer.

In particular, the polymer density in the photographic emulsion layer adjacent to the support is lower than the polymer density in other photographic emulsion layers, and the binder weight in the photographic emulsion layer adjacent to the support is 30% by weight or less. It is preferable that

The polymers of the invention may be added to the outermost layer of non-photosensitive gelatin, in which case the outermost layer preferably has a lower polymer density than any other layer of the photographic material.

The polymer may be added to the emulsion at any time, but it is suitably added after grain formation and before coating.

L11jX combination may be added as a powder, but! ~20
It is convenient to use it as a % aqueous solution.

Next, the cationic compound containing μ-class nitride used in the present invention will be described.

Among the cationic compounds used in the present invention, preferred are compounds represented by the following general formula CIA) or (nA).

General formula [IB] In the formula, R□ is an alkyl group having carbon number/-J4, carbon R2, R
3. R4 represents an alkyl group or a substituted alkyl group. 2
represents the atoms necessary to form a heterocycle. p represents l or co, and X represents an anion.

Preferred cationic compounds include, as a hydrophobic group, an alkyl group, an alkenyl group, or an alkylene group having 3 to lr carbon atoms, particularly preferably t to /r carbon atoms.

Specific examples of compounds are listed below.

H3 1-/j, 2Bre λαθ ■ 1-tj 0m8H3□-N(CI(3)3cPl-
16C2□H45-N(CH5)3Cj! el-1r(
C8H17)2・N(CH3)2BrθI-/ri(C0
2H25)2N(CH3)2αe1-2o C□, H
29-N(OH2CH20H)3Ctep+q=3 ■ 1-23 C1, H23CONH(CH2)3-N(
CH2) 3αe l-1≠ CH3 ■I I-! I CHCH80e Koαe 2αθ I-Kota 1-30 2Breλαe αe The compound represented by the general formula (IA) or (IB) of the present invention can be used in the range of io -to mol/m2, and is preferably 10 to 2× Preferably, it is added at a rate of 10'mol/m2. As for the addition method, it may be directly dispersed in a hydrophilic colloid, or it may be added after being dissolved in water or an organic solvent such as methanol or ethylene glycol. The scraps to be added may be added anywhere in the photosensitive material layer, but are preferably those of the general formula (II
) is preferably added to the layer adjacent to the support.

As the photosensitive silver halide used in the present invention, specifically, silver chloroiodide, silver iodobromide, silver chloroiodobromide, silver chloride, silver bromide, and silver chlorobromide can be used.

Silver iodobromide is preferably used. The content of silver iodide is preferably in the range of 3 to 30 mol %, particularly 7 to 20 mol %.

The average particle size is preferably 0.2 μm or more. The particle size distribution may be narrow or wide.

The silver halide grains in the emulsion may have regular crystal shapes such as cubic or octahedral, or irregular crystal shapes such as spherical or plate-like.
ar) or a composite form of these crystal forms. It may also consist of a mixture of particles of various crystalline forms. Furthermore, tabular grains having a particle diameter of 5 times or more the particle thickness are preferably used in the present invention.

Such tabular grains are described in U.S. Pat.

Da 3μ, Koko wo issue, Dou 3μ, Doug 3F, Core issue, Tokukai Sho! It is described in detail in the specifications of r-/27 Octopus No. 1, etc.

The photosensitive silver halide emulsion used in the present invention is P.
7 Me Ni Physique Photography (Chim) by Glafkides (P.
ie et Physique Photo-gra
phique ) J (Beaule Monte A, Pa
Published by u1M□ntel, 1947), G.F.
"Photographic Emulsion Chemistry" +) - (Photo by G, F, Duffin)
-graphic Emulsion Chemises
try) J (The Φ Focal Press The Fo
calPreSS, 1266), V. L. Zelikman et al.
Making and Coating Photographic Emulsion (Making andC
oating Photographic Emuls
ion) J (Focal Plex The poca
It can be prepared using the method described in I Press, Inc., 1996).

That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any of the one-sided mixing method, simultaneous mixing method, combination of seven methods, etc. good.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used.

According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Two or more types of silver halide emulsions formed separately may be mixed and used.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present.

As the photosensitive silver halide emulsion, a so-called primitive emulsion which is not chemically sensitized can be used, but it is usually chemically sensitized.

For chemical sensitization, for example, H.
H, Fr1eser)l @ 'Die Grunclla
Gen der Photography
nProzesse mit silver-ha
Akademische Verlagsgesll
The method described on pages A7j to 73μ can be used.

That is, a sulfur sensitization method using a compound containing sulfur that can react with silver ions or active gelatin, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds, etc. are used alone or in combination. be able to. As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used. As the reduction sensitizer, stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, etc. can be used. For noble metal sensitization, K may be a total complex salt, or a complex salt of a metal in Group I of the periodic table, such as platinum, iridium, or palladium.

Various compounds can be added to the above-mentioned photosensitive silver halide emulsion in order to prevent a decrease in sensitivity and generation of capri during the manufacturing process, storage or processing of the photosensitive material. Those compounds are goohydroxy-6-methyl-/, 3.3a,
A large number of compounds have been known for a long time, including 7-titrazaindene, 3-methyl-nzothiazole, /-phenyl-mercaptotetrazole, many polycyclic compounds, mercury-containing compounds, mercapto compounds, and metal salts. .

An example of a compound that can be used is described in "The Theory of the Photographic Process" by Mess.
In addition to citing the original literature in ``To-Graphic Process'' (3rd edition, / 4A), JP-A Akihirota No. 8'10211, to-tJot No. 8'10211, to-tJot No. O-/Herta, U.S. Patent No. J, r! 0. Any of the anti-fouling agents listed in No. AJ can be used.

The protective layer of the silver halide photographic material of the present invention is a layer consisting of a hydrophilic colloid, and the hydrophilic colloid used is one described above.

Further, the protective layer may be a single layer or a multilayer.

Various additives, supports and There are no particular restrictions on the manufacturing method and development method of the photosensitive material of the present invention, and JP-A-62-/J
! ≠≠Description in the specification of No. r and research disclosure, ltem /744tJ (/7 in the year/
February) or the same item /17/l (/ri7ri/1
month) can be referred to.

The relevant sections of these research disclosures are summarized below.

l Chemical sensitizer, page 23, page 6, right column 2 Sensitivity increasing agent, same as above 3 Spectral sensitizer, page 23-2, page 6, right column - supersensitizer 6≠ page right column 4, increase
Whitening agent 21 pages 5 Anti-fog agent 24t-2 ≠ page 6 right column and stabilizer 6 Part absorbent, fu, 2! ~ Page 2 Oto Geta right column ~ Ilter dye 6 Yo O left column Ultraviolet absorber 7 Anti-stain agent 2! Page right column tro page left ~
Right column 8 Dye image stabilizer Page 25 9 Hardener Colo page 6! /Page left column 10 Binder Ko page Same as above 11
Plasticizer, lubricant, 27 Sada 6!0 Right column 12
Coating aid, pages 26-27 Same as above Surfactant 13 Stateg corrective agent Page 27 Same as above 14 Color coupler 2g page 611
Page 7 to Unusual (Example) Next, the present invention will be specifically described based on Examples.

(Example 1) (1) Preparation of photosensitive silver halide emulsion Potassium bromide, potassium iodide, and silver nitrate were added to an aqueous gelatin solution with vigorous stirring to form a thick plate-like silver iodobromide emulsion with an average grain size/μ. (average iodine content io mol %) was prepared. Thereafter, it was washed with water by a conventional precipitation method, and then chemically sensitized by a gold/sulfur sensitization method using chloroauric acid and sodium thiosulfate to obtain a sensitized silver iodobromide emulsion. Sensitizing dye-l was added before chemical sensitization. Emulsion B (average iodine content 4 mol %) was prepared in the same manner as silver halide emulsion A, except that the amount of potassium iodide and the preparation temperature 'f were adjusted.

J, 0η/Ag1P (2) Preparation of coated sample Sample /-/J was prepared by sequentially providing each layer of the following formulation on a triacetyl cellulose support from the support side.

(Bottom layer) Binder: Gelatin lf/m2 Fixing accelerator: 0. /bu2/m2 dye: (CH2)2803K (CI-12)2803K
io-' mol/m2 (CH2) 2803K (CH2) 2803 to 10 mol/m2 Additive Compound of general formula (1) (listed in Table 1) (intermediate layer) Binder: Gelatin o, 4Lf/m'' coating Auxiliary agent: Poly p-styrene sulfonic acid potassium salt
r 119/m2 (emulsion layer) Coated silver amount: Emulsion A t, 3t/m2 Binder: Gelatin/, Jr/Ag1F dextran (
MW Approximately Hiroo, ooo) (listed in Table 1) Additive: C,8H350+CH2CH2U+2oH!
, rη/Agl? Trimethylolpronosulfonate oo■/m2 Coating aid: Potassium poly p-styrene sulfonate
7 x/m2 (Surface protective layer) Binder: Gelatin 0.7f/m2 Coating aid: 2~/m2 Hardener: /, -bis(vinylsulfonylacetamide) ethanco, JXlO'mol/m2 Matting agent: Poly Methyl methacrylate fine particles (average particle size 3μ) 0073~7m2 (4) Sensitometry These samples were stored for 7 days after coating at 24r0ctJ%H (D temperature and humidity).
After being exposed to light for 1/10 seconds using an OOlux tungsten source, the following treatment was performed.

(1) Automatic processor development Fill HPD developer (manufactured by Fuji Photo Film Corporation) to Persamat jAN automatic processor manufactured by Kodak, USA.-A
, j''Cgr t/min.The sensitivity of the processed sample was measured.

(11) Measurement of Sensitivity The sensitivity value was determined as the common logarithm of the reciprocal of the exposure amount necessary to obtain a transmission blackening density of fog+0.3.

(tft) We immersed the sample in distilled water (2 to 0C) for 3 minutes and then rubbed it with o and itp needles at different loads, and the load that caused scratches on the membrane surface was
It was rated at 2 as a measure of the intensity of the hit.

As can be seen from Table 7, samples containing dextran in the light-sensitive material and the compound of general formula (1) have very high sensitivity and high wet scratch strength.

Sensitivity was determined relative to sample/sensitivity as ioo.

(Example 2) Same as (1) Emulsion preparation example/ ((
2) Preparation of coated samples Each layer of the following formulation was sequentially provided on a triacetylcellulose support from the support side to prepare samples 13-1! It was created.

(Bottom layer) Same as Example/ (Middle layer) Same as Example/ (Emulsion -/) Coated silver amount: 1st emulsion (Emulsion B) /, 3? /m” Binder: Gelatin /, Ri2/m2 Dextran (MW approx. uo, ooo) o, 7f/m2 Additive: Cl8H350MoCH2CH2O+2oH!,
r■/Ag1S' Compound of general formula (1) Listed in Table 2 Coating aid: Poly p-styrene sulfone distribution IJ '7m salt 0, -2m
? /m 2 emulsion layer-2) Coated silver amount: 1st emulsion (emulsion A) μ, Coy 7m 2 Binder: Gelatin 7. 1/m2 Dextran (MW approx. 140.000) /, 197m” Additives: Cl8H350MoCH2CH2O+2oHs,
rη/Ag1r Trimethylolpropane 0OTI9/m2 Coating aid: Poly p-styrene sulfonic acid potassium salt
0.7/m2 (surface protective layer) Same as Example/(3) Sensitometry Same as Example 1 As shown in Table 1, the general formula is It can be seen that the sample containing the compound (1) has extremely high sensitivity and high wet scratch strength.

The sensitivity was determined relative to the sensitivity of sample 10 as 100.

Patent applicant Fuji Photo Film Co., Ltd. Procedural amendment 1, case description Patent application No. 30234 of 1939-2
'j No. 2, Title of the invention Silver halide photographic light-sensitive material 3, Relationship with the case of the person making the amendment Patent applicant contact information 〒10
6 Fujisha 11 Film Co., Ltd. Tokyo Head Office 7, 2-26-30 Nishi-Azabu, Central Tokyo (406) 2537 4. Subject of amendment The description in the "Detailed Description of the Invention" section of the specification & Contents of the amendment The description in the "Detailed Description of the Invention" section of the specification will be amended as follows.

/) Page 17, line 2θ "kara l" “karaλ” and correct it.

2) Page 17, line 2θ “70,000J “llθ, θ00J and correct it.

Claims (1)

[Scope of Claims] A silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer on at least one side of a support, the light-sensitive material comprising a repeating unit represented by the following general formula (II). 1. A silver halide photographic light-sensitive material, which contains a cationic compound containing quaternary nitrogen in the photographic emulsion layer or other constituent layers. General formula (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. 10
represents a substituted or unsubstituted alkyl group, aryl group or aralkyl group, which may be the same or different. Furthermore, R^2 and R^3 may be bonded to each other to form a nitrogen-containing heterocycle together with a nitrogen atom. L is an m+1-valent linking group. n is 0 or 1, and m is 1 or 2. )